Dyeable polypropylene fibers containing a phenol salt-amine complex and,optionally,a fatty acid salt



3,437,620 DYEABLE POLYPROPYLENE FIBERS CONTAIN- U.S. Cl. 26023 8 Claims ABSTRACT OF THE DISCLOSURE Polypropylene fibers modified with a metal phenolate derivative wherein the metal forms a coordinate bond with the nitrogen of ammonia, an aliphatic primary amine, an aromatic amine or a nitrogen-containing heterocyclic compound and, alternatively, modified also with a nickel or zinc carboxylate, which fibers possess superior affinity for dyestuffs capable of forming a coordinate bond with said metal.

This invention relates to dyeable polypropylene fibers which possess superior affinity for dyestuffs capable of forming coordinate bond with metals. More particularly this invention relates to modified polypropylene fibers containing metallo organic compounds consisting mainly of metal phenolate derivatives, and possessing superior affinity for dyestuffs capable of forming coordinate bond with the said metal and various superior properties as a textile fiber.

Though polypropylene fibers possess superior physical and mechanical properties, they are, on the other hand, hardly dyeable with the commonly known dyestuffs and dyeing methods because of their extremely hydrophobic and chemically inert property and the lack of dyeing sites having affinity for dyestuffs. In order to overcome this drawback, there have been proposed various methods; for example graft copolymerization of various vinyl monomers possessing affinity for dyestuffs onto polypropylene fibers, blend-spinning with high molecular or low molecular compound possessing affinity for dyestuffs, chemical treatment of polypropylene fibers so as to give dyeability, development of novel dyestuffs for polypropylene and so forth.

An object of the present invention is to provide polypropylene fibers possessing high grade of whiteness, superior dyeability and light fastness and high weather resistance while retaining various superior mechanical prop erties inherent to polypropylene.

The dyeing method which is characterized by incorporating an inorganic metal salt in fibers followed by dyeing with dyestuffs capable of bonding with the said metal has been known as mordant dyeing. However, since polypropylene possesses no affinity for inorganic metal salts, this method can hardly be applied to polypropylene fibers. Even applied, it is impossible to make a sufficient amount of metal salt be adsorbed onto polypropylene fibers from aqueous solution. On this account, dyeing achieved is of only light color, and the dyed products are easily discolored by washing or the like. Accordingly the dyed products possessing practical value cannot be obtained. If polypropylene were blended with an inorganic metal salt, this composition shows very poor spinnability or processability and gives no good fibers, because of the lack of affinity or compatibility between the metal salt and polypropylene. Furthermore since such inorganic metal salts generally promote decomposition of polypro- 3,43 'LGZQ Patented Apr. 8, 1969 pylene on heat or oxidation, it lowers weather resistance, heat resistance or oxidation stability of fibers.

British Patent 932,897 and United States Patent 2,984,- 634 disclosed the methods which are characterized by blending organic metal salts e.g. metal salts of higher aliphatic carboxylic acid such as nickel stearate, zinc stearate or the like. It is possible according to these methods to obtain fibers possessing superior fiber properties and good dyeability for dyestuffs capable of forming coordinate bonds with the metals. However fibers produced by these methods have only weak resistance against light, heat and oxidation. Accordingly these fibers readily lose their superior mechanical properties and so the practical value.

In order to obtain metal-containing dyeable polypropylene fibers having no such drawbacks we have made studies on various metallo organic compounds and found that fibers obtained by incorporating a compound represented by following general Formula I into polypropylene, followed by spinning, possess superior fiber properties, atfinity for dyestuffs capable of forming coordinate bonds with metals and weather resistance.

General Formula I n X @R O O/ In this general formula, R is an alkyl radical having from 4 to 18 carbon atoms, X is a member selected from the group consisting of S, SO, S0 CH and O and M is a metal selected from the group consisting of Ni, Zn, Co, Cu and Pb.

The melting points of the compounds expressed by the above-mentioned general formula are higher than the spinning temperature of polypropylene. Accordingly, these compounds must be finely ground on blending with polypropylene. When compounds ground to considerably fine powder are used, resulting fibers are passable as common dyeable fibers, but colored spots are observed in the crosssection of dyed fibers by microscope. This heterogeneity brings about some defects into the fibers and lowers their superior fiber properties.

According to the present invention, at least one of the compounds represented by following general Formula II is incorporated into polypropylene and subjected to spinning to solve the above-mentioned problems.

General Formula II 1 )2M1 (III) where R is an alkyl radical having from 7 to 29 carbon atoms and M is a metal selected from the group consisting of Ni and Zn. When one of the compounds represented by the general Formula. II is blended with poly propylene and subjected to spinning, it is also possible to improve whiteness and dyeability of fibers, brightness and various fastnesses of dyed products effectively by simultaneous use of at least one of the compounds represented by the general Formula III. Namely the object of the present invention can be attained by blend-spinning of polypropylene with at least one of the compounds represented by the general Formula II but also attained more effectively by adding at least one of the compounds represented by the general Formula III to the above-mentioned system.

The amount of compounds represented by the general Formula II to be added to polypropylene in the present invention is from 0.1 to 10 percent by weight preferably from 0.5 to 5 percent by weight of polypropylene. When the amount of addition is increased in this case, dyeability and weather resistance are improved but the amount of more than percent by weight is not favorable because it reduces various mechanical properties of fibers and increases the cost of the fibers. The amount of less than 0.1 percent by weight does not give improvement over unmodified polypropylene both on dyeability and weather resistance. By the addition of 0.1 percent by weight weather resistance can be improved but the improvement of dyeability is not sufiicient. For the purpose of improving both properties sufiiciently, the addition of more than 0.5 percent is necessary. According as the amount of addition is increased, the efiiciency of the added compound is lowered and the addition of more than 5 percent by weight does not show notable improvement over the addition of 5 percent by weight in the point of dyeability and Weather resistance. Considering the cost and mechanical properties of fibers, the addition of less than 5 percent is rather preferable.

The amount of compound expressed by the general Formula III to be added in the present invention is preferably from 0.5 to 5 percent by weight. When the improvement of the whiteness of fibers, and disperity of the compounds represented by the general Formula II are aimed at, the greater amount of addition may be preferable, but too much addition reduces mechanical properties of the fibers. Accordingly it is preferable to use as small an amount as possible. Generally speaking it is pref erable that the addition of compound represented by the general Formula III does not exceed that of compound represented by the general Formula II.

In the practice of the present invention, various common antioxidants for polypropylene such as phenol derivatives, amine derivatives or the like, synergistic agent such as dilauryl thiodipropionate, trioctadecyl phosphite or the like, titanium oxide, dispersing agent, surface active agent and other additives can be elfectively used. The production of fibers from polypropylene composition consisting of the compounds represented by the general Formulas II and III and above-mentioned additives can be carried out by any of the spinning processes, i.e. melt spinning process, dry spinning process and wet spinning process.

On the fibers produced by the present invention, dyestuffs which are capable of bonding with metals in the general Formula II by coordinate bond and/ or salt forming bond can be used. Namely the dyestuffs which are useful for the fibers produced by the present invention, besides those known generally as mordant dyes, include those which are developed particularly for polypropylene, containing no hydrophilic groups in their molecules and possessing such a group as to unite with metals by coordinate bond, e.g. o-hydroxyazo type, 8-oxyquinoline type, 4-hydroxythiazole type, o-hydroxyazomethyne type and hydroxyanthraquinone type dyestuffs. Representatives of such dyestuffs are National Polypropylene Dyes, Koprolene Dyes, Olefin Dyes and some of Mayfon Dyes and the like. On dyeing, customary methods can be used. If required, a dyeing asssitant such as non-ionic or anionic surface active agents or in some cases, cationic type surface active agent is used, dyeing is carried out at atmospheric pressure and under boiling while maintaining pH at from 2 to 8 (a weak acid is used as a controller). Then beautiful, bright colored objects having superior fastness can be obtained.

Representative compounds belonging to those represented by the general Formula II in the present invention are as follows: (Note: compounds shown hereinafter are those before coordinating the ligand B in the general Formula II.) Nickel salt of di-(2.2-dihydroxy- 5.5'-dibutyl) phenylsulfoxide, nickel salt of di-(2.2'-dihy droxy-5.5-dibutyl) phenylsulfone, nickel salt of di-(2.2- dihydroxy-5.5'-dibutyl) phenylmethane, nickel salt of di- (2.2'-dihydroxy-5.5-dibutyl) phcnylether, nickel salt of di- {(2.2'-dihydroxy-5.5'-di(1.1.3.3.-tetramethyl butyl) }phenylsulfone, nickel salt of di(2.2-dihydroxy-5.5'-di(1.1.3.3.- tetramethyl butyl)phenyl-sulfoxide, zinc salt of di{2.2'- dihydroxy-5.5-di-(1.1.3.3.-tetramethyl butyl) }phenyl sulfone, nickel salt of di-{(2.2-dihydroxy-5.5-di-(1.1.3.3.- tetramethylbutyl)}phenylmethane, nickel salt of di-{(2.2'- dihydroXy-5.5-di.\1.1.3.3.-tctramethylbutyl) }phenyl ether, nickel salt of di-(2.2'-dihydroxy 5.5'-dioctyl) phenyl sulfone, zinc salt of di-(2.2-dihydroXy-5.5'-dioctyl) phenyl sulfone, copper salt of di-(2.2-dihydroxy-5.5'-dioctyl) phenyl sulfone, cobalt salt of di-(2.2'-dihydroxy-5.5'-dioctyl) phenyl sulfone, lead salt of di-(2.2'-dihydroxy-5.5- dioctyl) phenyl sulfone, and nickel salt of di-(2.2'-dihydroxy-5.5'-dilauryl) phenyl sulfoxide.

Representative compounds which coordinate to abovementioned compounds and belong to nitrogen-containing compound, i.e.'ligands B in the general Formula II are as follows; butylamine, octylamine, laurylamine, stearylamine, ethylene diamine, hexamethylene diamine, aniline, phenylene diamine monoethanol amine, pyridine, quinoline and the like.

Such compounds expressed by the general Formula II can be synthesized readily by common synthetic methods of organic chemistry. For example from p-1.1.3.3.-tetramethyl butylphenol and sulfurchloride, di-{2.2-dihydroxy- 5.5'-di-(1.1.3.3.-tetramethylbutyl)} phenyl sulfide can be obtained. If oxidized with hydrogen peroxide, sulfoxide or sulfone is obtained according to a number of moles of hydrogen peroxide used and reaction condition. Di-{2.2'- dihydroxy 5.5 di-(1.1.3.3.-tetramethylbutyl)} phenyl methane is obtained from salicyl alcohol by alkylating the latter with isobutylene, and heating the resulting 2-hydroxymethyl-S-(1.1.3.3.-tetramethylbutyl) phenol with pl.l.3.3.-tetramethylbutyl phenol. Resulting phenol derivative is allowed to react with metal salt of inorganic acid or of acetic acid to produce metal salt of phenol. If such metal salt of phenol and nitrogen-containing compound (B) are heated and reacted in the medium such as ethanol or the like, the nitrogen atom forms coordinate bond with the metal atom to produce a compound represented by the general Formula II.

Representatives of the Compounds represented by the general Formula III are as follows; zinc stearate, nickel stearate zinc laurate, nickel laurate and the like.

The invention is illustrated but not limited by the following examples.

Example 1 A compound (A) produced by coordinating butyl amine to nickel salt of di-(2.2'-dihydroxy-5.5'-dibuty1) phenyl sulfone and zinc stearate (B) were admixed with crystalline polypropylene having an intrinsic viscosity of 1.4 (measured in tetraline at a temperature of 135 C.) in such proportions as shown in Table 1. Further an oxidation stabilizer was added. The resulting mixture was made into pellets at a temperature of 220 C., subjected to spinning at a temperature of 260 C. according to the customary melt-spinning process and resulting filaments were stretched 5 times the original length at a temperature of C. The filaments were subjected to scouring, dyeing and soaping according to the following condi 6 tions of (a), (b) and (c). Properties of fibers and results exposure of a weather-o-meter for 300 hours. Retention of of dyeing are showninTable 1. tenacity were as follows: No. 1, 90%; N0. 2, 93%; and (a) scouring condition: No. 3, 54%; dyeable polyproplene fibers of the present Bath: invention proved their superiority. Scourol #400 g./l 0.5 5 Example 2 -p f p Compounds produced by coordinating butyl amine Liquor ratio a 1350 (D), lauryl amine (E), hexamethylene diamine (F), T'mPerature 70 aniline (G) and pyridine (H) to nickel salt of di-{2.2- Tlme dihydroxy-5.5-di(1.1.3.3-tetramethylbutyl)} phenyl sul- After treated, filaments were washed with w ater, dried, l0 fone (C) were admixed with crystalline polypropylene and subjected to dyeing. having an intrinsic viscosity of 2.2 in proportions of (b) Dyein condition: each 1.5 percent by weight respectively. Filaments were Dyestuif (National Polypropylene Dark Blue produced and dyed by the same method as in Example 1.

2BM) 5 percent OWF Various properties measured are shown in Table 2.

TABLE 2 Dry Elongation Exhaustion Fastness (grade) No. Additives strength (percent) (percent) (g./d.) Light Washing It is presumed that this dyestuif has the following chemical 5 Symbols in the column of additives mean that the comstructural formula: pound C was coordinated with ligands corresponding to H0 the letters D-H. No. 4 is a control. H502 When the cross sections of dyed filaments thus produced CN=N were observed, under a microscope, dyed points in the filaments No. 4 were spotted, but in other filaments the N dyeing was carried out evenly and there were no such Dispersing agent: spots observed. The color tones of dyed products other Mypo D g./l 1 than No. 4 were all bright. Glacial acetic acid g./l 0.2 Liquor ratio 1:50 Example 3 Temperature Zinc salt of di-[2,2'-dihydroxy-5,5'-di-(1,1,3,3-tetra- After dyeing, filaments were washed with water and methylbutyl)] phenyl sulfone (I) and nickel stearate (I) SllbjCCtBd to soapmg.

were admixed with crystalline polypropylene having an sfiaping zg) A 0 5 40 intrinsic viscosity of 1.4 in such proportions as shown in Swill-o1 Table 3. Further antioxidant and synergestic agent were Sodium carbonate g./l 0.1 Liquor ratio e Fllarnents were obtained as in Example 1, Uslng Temperature C N i n l Polypropylene Brilliant Violet 3RM as a dyei minutes 20 45 stuif-it is presumed that this dyestuif has the following After treated, filaments were washed with water and chemical structural formula: dried.

TABLE 1 Whit Fa tness gni r i) Dry;1 1 Dir-y (peta s? lzfixhausgon (grade) I? 811C911 M A B the. 3330511?) Y PI p Light Washing o 5.41 300 80.5 93.0 94 4-5 0 5 5.62 28 0 80.9 96.4 95 4-5 0 1 0 4.93 32 4 82.2 90.0 89 3 5 1 More than 6.

The whiteness was measured by a recording spectropho- H? tometer and expressed by values of Y and PI, the light 0 fastness was determined by the carbon arc method (fadeometer) according to Japanese Industrial Standard N JIS-L-l044 (1959) and the washing fastness was by the beaker method BC2 cc r i g o 1154-4045 the same dyeing experiments as in Example 1 were car- Further these three kinds of filaments were subjected to 6 ned out. The results were shown in Table 3.

TABLE 3 Additives (percent) Dry Elongation Exhaustion Fastness (grade( M sgreridggh (percent) (percent) 1 More than 6.

8 In Table 3, Nos. 10, 11 and 12 were controls. that the whiteness of filaments prior to dyeing was partic- Though in No. 10 the exhaustion is considerably imularly improved. proved when compared with No. 10, the exhaustion in Example 6 No. 10" is not so much improved when compared with No. 10'. It is seen from this fact that by coordinating amine to (I), the dispersibility of (I) in polypropylene is improved and as a result the dyeability is improved, but such effect is not considerably influenced by the amount of amine to be coordinated to (I). Compared with the case of No. 10, the light fastness was increased in the Melting points of nickel salts of di-{2.2'-dihydroxy 5.5'-di- (1.1.3.3.-tetramethy1butyl)} phenyl sultone coordinates with various nitrogen-containing compounds were measured, of which the result is shown in Table 7.

TABLE 7 case of No. 11. Though the brightness of color of dyed Nitrogemontammg Melting points a products was low in No. 12, it was high in N0. 11. compound N b 2 Examp 1e 4 l None 360 ldsing a compound (K) obtained by COOI'dII'IHUHg bUiYlg: fi gfg g amine to the compound (I) in Example 3 and with the 4 Stearylamine 00-64 same other condition as in Example 3, filaments were glexamethvlmd 280495 yridme 210-220 produced and sub ected to dyeing experiments whereby the 7 Aniline 165-i70 result shown in Table 4 was obtained.

TABLE 4 Additives Dry No. (percent) strength Elongation Exhaustion Fastness (grade) (g./d.) (percent) (percent) Light Washing The cross sections of dyed filaments shown in Table 4 We claim: were observed under a microscope and compared with 1. Dyeable polypropylene fibers consisting of polythe result of Nos. 10 and 11 in Example 3. In No. 10 propylene and from 0.1 to 10 percent by weight of at and 11, dyed points were distributed in spots. Particleast one kind of modifying agent represented by general ularly in No. 10 the dyestutf was adsorbed only on these Formula II.

points. On the other hand the whole cross sections were dyed evenly in the cases of Nos. 13 and 14 and the-re R were observed no spots. In the case of No, 12 in Exam- 5 ple 3 there was a tendency of ring dyeing though no spots were observed. It was clarified, accordingly, that the 0 present method was much more superior than that of Nos. 10 and 11 g Example 5 wherein R is an alkyl radical having from 4 to 18 carbon atoms, X is a member selected from the group consisting of 80, S0 CH and O, M is a metal atom selected from the group consisting of Ni, Zn, Co, Cu and Pb, B is a member selected from the group consisting of NH aliphatic primary amines, aromatic amines, and nitrogencontaining heterocyclic compounds and n is an integer of 1 or 2. H0 2. Dyeable polypropylene fibers consisting of polypropylene and from 0.1 to 10 percent by weight of at least R C N=N Q one kind of modifying agent represented by general Formula II and from 0.5 to 5 percent by weight of sup- N plementary modifying agent represented by general For- Compounds shown hereinafter (M-O) and zinc stearate (B) and further antioxidants were admixed with crystalline polypropylene having an intrinsic viscosity of 2.2. Filaments were produced as in Example 1 and using 45 as a dyestutf Olefin Violet 1561 --it is presumed that this dyestutf has the following chemical structural formula:

The dyeing experiments were carried out as in Example mula III (R COO) M wherein R is an alkyl radical 1 whereby the results shown in Table 5 were obtained. having from 7 to 29 carbon atoms and M is a metal TABLE 5 Additives Dry Elongation Whiteness Exhaustion Fastness (grade) (percent) strength (percent) (percent) (g./d.) Y (percent) PI (percent) Light Washing 6 26. 0 77 7 90. 5 79 More than 6-.. 4 s 78 25.1 81 2 96.1 86 d 5 s 42 29.8 79 9 91.8 89 4-5 6 as 27.5 80 Q 92. 2 4-5 Alphabets M, N, 0 in the column of additives in Table 65 atom selected from the group consisting of Ni and Zn.

5 indicate following compounds: 3. Dyeable polypropylene fibers according to claim 1 M nickel Salt of 1 3 3 wherein the amount of modifying agent is from 0.5 to 5 percent by weight.

tetr meth l but l hen l sulfoxid coordinat d with but; amiiie, y P y e e 4. Dyeable polypropylene fibers according to claim 2 N-nickel salt of di-2.2'-dihydroxy-5.5'-di-(1 1 3,3 7 wherein X is a member selected from the group consisting tetramethyl butyl) phenyl methane coordinated with butyl of SO 2 M is a metal 3mm Selected from the amine, group consisting of Ni and Zn, B is a member selected O-nickel salt of di-{2.2'-dihydroxy-5.5-di-(l.l.3.3- f m t group Consisting of NH aliphatic primary tetramethyl butyl)} phenyl ether coordinated with butylamine, aromatic amine, nitrogen-containing heterocyclic amine. It was observed in the case of Nos. 16 and 18 7 compound, 11 is an integer of 1 or 2.

5. Dyeable polypropylene fibers according to claim 2 wherein X in general Formula II is S M in general Formula II is Ni, B in general Formula -II is nitrogencontaining heterocyclic compound and M in general Formula 111 is Zn.

6. Dyeable polypropylene fibers according to claim 1 wherein B in general Formula II is a member selected from the group consisting of butyl amine, lauryl amine, stearyl amine, hexamethylene diamine, pyridine and aniline.

7. Dyeable polypropylene fibers according to claim 2 wherein B in general Formula II is a member selected from the group consisting of butyl amine, lauryl amine, stearyl amine, hexamethylene diamine, pyridine and aniline.

8. Dyeable polypropylene fibers according to claim 5 wherein B in general Formula II is a member selected from the group consisting of butyl amine, lauryl amine, stearyl amine, hexamethylene diamine, pyridine and aniline.

1 0 References Cited UNITED STATES PATENTS 2,448,799 9/1948 Happoldt et al. 260-23 2,971,940 2/1961 Fuchsman et al. 260 45.75 5 2,984,634 5/1961 Caldwell et al 260-23 3,072,601 1/1963 Breslow 26045.75 3,163,492 12/1964 Thomas 855 3,215,717 11/1965 Foster 260-439 3,238,189 3/1966 May et a1 260-207 3,240,552 3/1966 Joyner et a1. 839

FOREIGN PATENTS 932,897 7/ 1963 Great Britain.

15 DONALD E. CZAJA, Primary Examiner.

R. A. WHITE, Assistant Examiner.

US. 01. X.R. s ss; 260 45.15,93.7, 94.9 

